Nuclear Instruments and Methods 209/210 (1983) 57-61 57

North-Holland Publishing Company

A M O D E L OF T H E S U R F A C E B I N D I N G ENERGY FOR fcc C O P P E R - N I C K E L ALLOY

G. W i l l i a m R E Y N O L D S
State University of New York at Albany, Albany, NY 12222, USA

An empirical model partitioning the surface binding energy among the three sets of nearest neighbors is presented for the face
centered cubic lattice. The surface binding energy is then determined for each atom in the surface for the 100, 110 and 111 surface
planes of a small uniform alloy crystal with surface atomic fractions attainable by ion implantation of the minor component into a
pure elemental target. These surface binding energies per atom are then summed over the crystal surface and an average surface
binding enery per atom is determined to ascertain the effect on the partial sputtering yields of each component in the alloy layer
produced by ion implantation. The partial sputtering yield so calculated is compared with experimental data. This model has
neglected the effect of the modified nuclear stopping power due to the ion implantation.
The modified average surface binding energy as determined by these calculations does predict a shift in the partial sputtering yields
toward the reported experimental values. A visual model of the modified energy surface suggests a higher probability for particular
atoms to be sputtered from the surface leading to more pronounced modification of the average surface binding energy.

1. Introduction ergy for a t o m s in the surface will cause the net a n d

T h e m o d i f i c a t i o n of metallic surfaces t h r o u g h
the use of ion b e a m t e c h n o l o g y is r a p i d l y b e c o m -
ing an accepted technique for the p r o d u c t i o n of
specialized alloy surfaces in industrial a p p l i c a t i o n s
[1]. C u r r e n t theoretical discussions a n d recent re-
views of the s p u t t e r i n g process d o not discuss the
i m p o r t a n c e of the effect of the c h a n g i n g a t o m i c
surface fractions on the total s p u t t e r i n g yield for
the target m a t e r i a l [2-8]. In a recent p a p e r b y
R e y n o l d s et al. [9] a n d earlier p a p e r b y H a f t a n d
Switowski [4] were p r e s e n t e d m o d e l s to include the
effect of the m o d i f i e d surface on the d e v e l o p m e n t
of the final surface c o m p o s i t i o n . In this p a p e r the
a u t h o r calculates the average surface b i n d i n g en-
ergy for the alloys of c o p p e r a n d nickel as a
function of the fraction of the m i n o r c o m p o n e n t in
the surface a n d c o m p a r e s the net a n d p a r t i a l
s p u t t e r i n g yields for the target m a t e r i a l with cur-
rent e x p e r i m e n t a l evidence.
2. Surface energy calculation
M o d e l s simulating the b e h a v i o r a n d origins of
s p u t t e r e d particles from metallic surfaces indicate
that the s p u t t e r e d particles originate from the first
few layers from the surface of the target m a t e r i a l
[10]. Therefore, p e r t u r b a t i o n s in the b i n d i n g en-
p a r t i a l sputtering yields for the target m a t e r i a l to
change d u r i n g ion i m p l a n t a t i o n a n d alter the de-
v e l o p m e n t of the surface layer. In o r d e r to de-
termine the m a n n e r in which the surface b i n d i n g
energy of the crystalline surface changes, m o d e l s
of the 100, 110, a n d 111 planes of the face centered
cubic lattice were constructed. The m o d e l s were
four to six atomic layers in d e p t h and the surface
layer c o n t a i n e d a p p r o x i m a t e l y 900 atoms. The im-
p l a n t e d species were i n t r o d u c e d into the crystal in
lattice sites u n i f o r m l y d i s t r i b u t e d t h r o u g h o u t the
structure in c o n c e n t r a t i o n s p r o d u c i n g a t o m i c
surface fractions of 0.01, 0.02, 0.03, 0.04, 0.05 a n d
0.10. F r o m e x a m i n i n g the lattice structure so al-
tered the intereaction p a r a m e t e r s for the first three
sets of nearest neighbors were d e t e r m i n e d for each
surface atom. F r o m the literature [11-15] the
surface b i n d i n g energies for the initial target
material a n d the b e a m species were o b t a i n e d for
subsequent calculations.
The interaction p a r a m e t e r s for each type of
nearest n e i g h b o r interaction were d e t e r m i n e d as
follows:
Ul N2 N3
~y+~2y+-~3y= l, (1)
where y is the i n t e r a c t i o n fraction, ~ is the n u m -
b e r of n e i g h b o r s in the set, a n d X i is the interac-
tion d i s t a n c e for the set with the lattice spacing

0167-5087/83/0000-0000/$03.00 © 1983 N o r t h - H o l l a n d I. THEORY

 58 G. W, Reynolds / Surface binding energy for fcc Cu- Ni allqv

equal to one. Table 2

Binding energy per interaction
I, =yX~, (2)
where I, is the interaction parameter for that set, Type Ni-Ni Cu-Cu Cu-Ni
(eV) (eV) (eV)
and it follows that
E N , I, = 1. (3) 100 plane set 1 0.30060 0.25022 0.27540
100 plane set 2 0.21255 0.17693 0.19476
The binding energy per nearest neighbor interac- 100 plane set 3 0.17355 0.1446 0.15901
tion now becomes 110 plane set 1 0.46976 0.39162 0.43207
110 plane set 2 0.33215 0.2769 0.3055
B, = /do/,, (4) 110 plane set 3 0.27119 0.22608 0.24943
where B~ is the binding energy per neighbor inter- 111 plane set 1 0.33206 0.27523 0.30365
action and U0 is the surface binding energy per 111 plane set 2 0.23478 0.1946 0.21469
atom for initial materials. 111 plane set 3 0.19169 0.15889 0.17529
Table 1 tabulates the interaction parameters for
each nearest neighbor site in each of the three
surface planes. Table 2 tabulates the binding enery during the implantation process can be determined
per interaction for the nearest neighbors for each using the expression
type of interaction in the copper-nickel system. Stot = ~-"~n,f,S(1),. (6)
For each atom in the surface layer the binding
energy for each interaction of the nearest neighbor Sto t is the net sputtering yield for the target at
sets was tabulated and summed over the entire any time during implantation, n, is the atomic
surface layer and then divided by the total number surface fraction of each component, S(1)~ is the
in the layer to obtain an average surface binding elemental sputtering yield for each component,
energy (U~vs) corresponding to that atomic surface and f, is the surface binding energy correction
fraction. Uavs was then plotted versus the fraction factor as discussed by Reynolds et al. [9]. The
of the implanted species. From the graph it was factor
noted that u0
f' = Uav (7)
U(T)avg = U(A)o + nB(U(B)0 -- U ( A ) 0 ) . (5)

U(T) is the average surface binding energy for the
target, U(A)o is the initial surface binding energy
for the target, U(B)o is the surface binding energy
for the implanted species, and n s is the atomic
surface fraction of the implanted species.
The net sputtering yield for the target surface
effectively introduces the new average surface bin-
ding energy into the calculation of the sputtering
yield for the target. Expanding eq. (7) by substitut-
ing Udvg from eq. (5),
U(A)o
f, = U(A) ° - nr)(V(S) ° - U ( A ) o ) , (8)

Table 1
Interaction parameters for face centered cubic crystal lattice

Crystal plane 100 110 111

First neighbor lattice spacing gr2~ l 2v/~l 2vff/2 l

N u m b e r in first neighbor set 8 7 9
First interaction parameter ( I I ) 0.05416 0.09163 0.05919
Second neighbor lattice spacing 1 ! /
N u m b e r in second neighbor set 12 2 3
Second interaction parameter (12 ) 0.03830 0.06500 0.04185
Third neighbor lattice spacing 6Vt6/2 l
N u m b e r in third neighbor set 12 6 10
Third interaction parameter ( 13 ) 0.03127 0.05307 0.03417
 G. 14/. Reynolds / Surface binding energy for fcc Cu Ni alloy - 59

multiplying by unity Applying eq. (10) and (6) one can calculate the
U(A)o (U(A)o - n B ( U ( B ) o - V(A)0 ) net sputtering yield for the target and the partial
f~= (9) sputtering yields for each component using either
U(A)2o - n ~ ( U ( B ) o - U(A)o) 2 ' calculated elemental yields from theory or yields
which reduces to determined from experiment. Figs. l(a) and (b)
compare the net sputtering yields so calculated
nB(U(B)o- U(A),) with the average surface binding energy versus
f,= 1 U(A) ° , (10)
atomic surface fraction of the implanted species.
using the a p p r o x i m a t i o n t h a t the surface f r a c t i o n Elemental sputtering yields used in these figures
n B is less than one and the square of the term is are from the literature [9,16].
much less than one.

3. The experiment
e.V%tom

' NET SPUTTERINGYIELD / /

Pure polycrystalline elemental samples of nickel
(~o370~- - - - - EAVER~GyESURFACE BINDING / and copper were respectively implanted with
~. J - - - - - STEADY STATE SURFACE / copper and nickel ions at 90 keV energy moni-
L. FRACTION / 4.70 ~
toring the optical emission of both the implanted
species and target element throughout the implan-
9 I / I cl tation process. When the steady state condition
' /%. } 4.60

o3
1 . 0 - - ~ -- COMPUTERCALCULTED
x - ~ ~,,~,. " .... OPTICALMONITOR
..~..I ---- CLEAN SURFACEOPTICAL
i / ~.. "x" EXPERIMENTALBY FOIL(9

~50 ~
, I , .J, ~ I I
0 I .2 ,3
a ATOMIC SURFACE FRACTION FOR BEAM ATOMS

u
e.v/otom

\~ -- NET SPUTTERING YIELD 5.40

\ --- AVERAGE SURFACE BINDING
l- ENERGY
\ - - - STEADY STATE SURFACE ~°,c'/'l
FRACTION
\ 50 so 7 e 9 io ~o 3~6-
4.00 FLUENCE OF BEAM ATOMS x lO is ions/cm z
o> a
,9 \
5.30
N\ bJ
--COMPUTER CALCULATED
w
...... OI~'ICAL MONITOR
~- " x" EXPERfME ............. X.............
z
~, 3.9o
h-
\\\\'I 5.20
tlJ

o~
u.

5.10
i 1 i . I ,
k 0 I 2 .3
K# ATOMIC SURFACE FRACTION FOR BEAM ATOMS
0,0 , : r-L . . . . . . ~ = ~ ~ J , L I I
.6 7 8.9 IO 2 3 4 5 6 7 8 9 IO 2~) 30
Fig. 1, Comparison of the average surface binding energy and b FLUENCE OF BEAMATOMS x I01eions/cma
the net sputtering yield for (a) a copper target with the increas-
ing atomic surface fraction implanted nickel ions at 90 keV, (b) Fig. 2. Development of the atomic surface fraction of (a) copper
a nickel target with the increasing atomic surface fraction and (b) nickel with respect to fluence for 90 keV nickel ions
implanted copper ions at 90 keV. implanted into a copper target.

I. THEORY
60 G. W. Reynolds / Surface binding energy for f c c Cu - Ni alloy

was observed (small or no change in the optical planted species and the initial target species as a
signals for the sputtered material) collector foils function of fluence of beam atoms. The computer
were introduced to collect the sputtered material calculated curve illustrates the predicted surface
from the target under these conditions. The experi- whereas the optical monitor curve shows the devel-
mental equipment and associated analytical equip- opment of the surface as indicated by the intensity
ment have been described previously [18,19]. The of the light emitted by excited neutral atoms
optical data collected and the results of the analy- sputtered from the target surface. The isolated
sis of collector foils from this experiment and points are results from the analysis of the quantity
previous experiments have been plotted with re- of sputtered material collected on pure aluminum
spect to the fluence. The surface fraction versus foils in this fluence region of the implantation. The
the fluence as calculated by the computer program optical signals for the beam species were normal-
developed from the model discussed by Reynolds ized using a pure elemental target as reference
et al. [9] is plotted as a reference for comparison of during the implantation. The initial target signal
experimental results with predicted computer val- was used to normalize the target signals during
ues. The sputtering program was developed at the implantation. Applying eqs. (10) and (6) to the
Naval Research laboratory by Davisson [17]. steady state observations and to corresponding
intermediate states, the net sputtering yields so
calculated compare favorably with figs. l(a), (b).
4. Results
Figs. 2(a), (b) and 3(a), (b) display the develop-
ment of the atomic surface fractions of the ira- 5. Summary

. . . . ~"~-~ -- COMPUTER CALCULATED The surface binding energy per atom is appor-
~" , ~ . .... OPTICAL MONITOR
• -' " ---- CLEAN SURFACEOPTICAL tioned to the first three sets of neighbors in pro-
0z ......... ' " ' IMINT BY FOIL(9)
portion to the interaction distance for the face
.9 "'.
centered cubic crystal lattice. The average surface
binding energy per atom is determined for con-
centrations of implanted atoms corresponding to
concentrations observed in experimental implanta-
m
B tions. The copper-nickel system was selected to
test the calculations. The results indicate: (1) that
<
when a pure elemental target is implanted with a
second element, the average surface binding en-
!6 ~B,.O ~' ; ~ ; ; ~ 9 , o, I
2'o ergy of the modified target material changes in the
FLUENCE OF BEAM ATOMS x 1016ions/cm 2
a direction of the energy of the implanted species;
0.3 (2) that this method of apportioning the surface
-- COMPUTER CALCULATED
...... OPTICAl_ MONITOR binding energy gives a linear dependence to both
"x" EXPERIMENT BY FOIL (9) ~,.. ..... the changing surface binding energy and the net
sputtering yield for the target during ion implanta-
tion; (3) that a simplified binding energy correc-
E x
tion factor may be used with theoretical or experi-
mental elemental sputtering yields to determine
¢noi steady state of an ion implantation in which one
element is implanted into a second elemental
target; and (4) that recent experimental results
measuring the atomic surface fractions and the
.6 1.8.9tO 2 3 4 5 6 7 910 20 3~ corresponding partial and net sputtering yields
FLUENCE OF BEAM ATOMS x I016 ions/crn = agree favorably with the calculations presented for
b
Fig. 3. Development of the atomic surface fraction of (a) nickel the copper-nickel system.
and (b) copper with respect to fluence for 90 keV copper ions Additional systems need to be examined to
implanted into a nickel target. verify the application of these calculations to a
 G.W. Reynolds / Surface binding energy for fcc Cu-Ni alloy
wider group of materials modified by ion implan-
tation. Currently experiments have been per-
formed implanting a body centered cubic crystal
lattice and implanting a binary alloy of known
composition with a metallic ion beam. When the
analysis of these experiments is completed addi-
tional information will be available to test this
form of energy calculations.
Special recognition should go to the Sputtering
Research Group of the Materials Modification
Branch of the Condensed Matter and Radiation
Effects Division, Naval Research Laboratory,
Washington, D.C. for their support and experi-
mental data relative to the copper/nickel system.
References
[1] J.K. Hirvonen, ed., Treatise on materials science and
technology (Academic Press, New York, 1980).
[2] P. Sigmund, Sputtering by ion bombardment, ed. R.
Berisch (Springer-Verlag, Berlin, 1980) ch. 2.
[3] H.H. Anderson and H.L. Bay, Sputtering by ion bombard-
ment, ed., R. Berisch (Springer-Verlag, Berlin, 1980) ch. 4.
61
[4] P.K. Haft and Z.E. Switowski, Appl. Phys. Lett. 29 (1976)
549.
[5] P.K. Haft, Appl. Phys. Lett. 31 (1977) 259.
[6] H.H. Anderson, Sputtering of multicomponent metals and
semi-conductors, SPIG 1980, ed., M. Matini (Boris Kidric
Institute of Nuclear Physics, Yugoslavia), p. 421.
[7] P. Sigmund, J. Vac. Sci. Technol. 17 (1980) 396.
[8] R. Collins, Rad. Effects 37 (1978) 13.
[9] G.W. Reynolds, F.R. Vozzo, R.G. Alias, A.R. Knudson,
J.M. Lambert and P.A. Treado, Metastable materials for-
mation by ion implantation, eds., S. Picraux and W.
Choyke (Elsevier New York, 1982) p. 51.
[10] D.E. Harrison, Jr., P.W. Kelly, B.J. Garrison, and V.
Winograd, Surf. Science 76 (1978) 311.
[11] D.P. Jackson, Rad. Effects 18 (1973) 185.
[12] K.A. Gschneider, Sol. St. Phys. 16 (1964) 275.
[13] M. Ackerman, F.E. Stafford and J. Drowart, J. Chem.
Phys. 33 (1960) 1784.
[14] M. Guido, G. Gigli and G. Balducci, J. Chem. Phys 57
(1972) 3731.
[15] D.L. Hildebrand, Chem. Phys. Lett. 15 (1972) 379.
[16] R.G. Alias, A.R. Knudson, J.M. Lambert, P.A. Treado
and G.W. Reynolds Nuc. Instr. and Meth. 194 (1982) 615.
[17] C. Davisson, Private communication (Memorandum re-
port, to be published, Naval Research Laboratory).
[18] G.W. Reynolds, A.R. Knudson and C.R. Gossett, Nucl.
Instr. and Meth. 182/183 (1981) 179.
[19] R.G. Allas, A.R. Knudson, J.M. Lambert, P.A. Treado
and G.W. Reynolds, Nucl. Instr. and Meth. 194 (1982)
615.
I. THEORY